A New Process for Removing Calcium from

Crude Oils Containing Calcium Naphthenates

Scott Bieber
Baker Petrolite
Sugar Land, TX

Crude Oil Quality Group

Millennium Knickerbocker Hotel, Chicago
May 26, 2005
 Agenda

Problems caused by high calcium crude oils

Overview of the EXCALIBUR process

Benefits of EXCALIBUR technology

Field performance data

Conclusions

Copyright 2005 Baker Petrolite Corporation. All rights reserved

High Calcium Crude Oils

What are some of the crude oils that contain

calcium naphthenates?

West Africa (Doba, Kuito)

North Sea (Heidrun, Captain)

China (Bohai Bay, Shengli)

Indonesia (Serang)

Copyright 2005 Baker Petrolite Corporation. All rights reserved

Problems Caused by High Ca Crude Oils

Tank Farm problems

Calcium naphthenates are natural emulsion
stabilizers
High BS&Ws in oil charged to crude unit
Desalting problems, when metals are present as
naphthenate salts or fine particulates
High conductivity causes voltage loss
Emulsion stabilization
Water carryover
Poor effluent water quality (high O&G can
impact waste water treatment plant)
Desalter effluent water exchanger scaling
Calcium deposits

Copyright 2005 Baker Petrolite Corporation. All rights reserved

Problems Caused by High Ca Crude Oils

Crude unit corrosion

Most high Ca crudes also high in total acid
number (TAN)
Atmospheric tower overhead corrosion control
High organic acid loading in overhead system
can increase neutralizer demand

Increased probability of high temperature

naphthenic acid corrosion

Copyright 2005 Baker Petrolite Corporation. All rights reserved

Problems Caused by High Ca Crude Oils

High Ca levels in residual streams

FCCU catalyst deactivation, if resids are fed
to the FCCU or RFCCU
Higher coke Ca content
May not be able to make anode grade coke
Higher heavy fuel oil Ca content
New ISO-8217 specs will include maximum
Ca levels in HFO; some fuel oil traders and
end users already measure Ca
Increased slagging in furnaces burning
refinery fuel oil

Copyright 2005 Baker Petrolite Corporation. All rights reserved

EXCALIBURSM Metals Removal Technology

EXCALIBUR: A Process for Removing Calcium

from Crude Oil in Crude Unit Desalting
Operations
Developed by Baker Petrolite for a major oil
company
Designed for crude oils high in calcium
naphthenates (> 100 ppm as Ca)
May also remove inorganic iron compounds,
or iron present as naphthenate salts
Does not remove nickel or vanadium
Proven, industry-leading technology already
used in Europe, US and Asia

Copyright 2005 Baker Petrolite Corporation. All rights reserved

EXCALIBUR Metals Removal Technology

Process Overview
Inject metals complexing agent into desalter
wash water
Maintain high mixing energy to promote good
contact of water/complexing agent and oil
Complexing agent converts metallic species
such as Ca, Fe naphthenates into water
soluble compounds
Solubilized metals partition into the aqueous
phase and are removed with desalter effluent
water
Naphthenic acids stay in the crude oil

Copyright 2005 Baker Petrolite Corporation. All rights reserved

EXCALIBUR Metals Removal Technology

Treated Crude Oil

to Hot Preheat Train

Crude Oil
Desalter
Storage

Mix Valve

Wash Water to
Desalter

Emulsion
Breaking Chemical

Desalter
Metals Effluent Water
Complexing Agent to WWTP

Calcium Scale Inhibitor

Copyright 2005 Baker Petrolite Corporation. All rights reserved

EXCALIBUR Metals Removal Technology

Benefits of Using EXCALIBUR Metals Removal

Technology
Up to 85% calcium removal efficiency
achieved in field applications
Allows processing of higher rates of high
Ca crude oils
Increased refinery margins when crudes
are purchased at a discount
Reduces calcium levels in atmospheric,
vacuum resids
Minimizes FCCU catalyst degradation
Reduced Ca levels in coke and heavy fuel oils
Reduced boiler, heater tube slagging

Copyright 2005 Baker Petrolite Corporation. All rights reserved

 EXCALIBUR Field Evaluations

European Location
30 - 120 ppm Ca in crude blend (15%
Doba), 62 ppm average
Program target is < 20 ppm Ca in
desalted crude
Average Ca removal efficiency 70%
85% Ca removal achieved when desalter
effluent pH < 6
Reduced Ca levels allows refinery to
feed atmospheric resid to FCC

Copyright 2005 Baker Petrolite Corporation. All rights reserved

EXCALIBUR Field Evaluations

USA Location
Up to 50 ppm Ca in crude blend (15%
Doba typical)
< 10 ppm average Ca in desalted crude
Ca removal efficiency averages 70%
Reduced Ca levels allows refinery to
feed atmospheric resid to FCC

Copyright 2005 Baker Petrolite Corporation. All rights reserved

 EXCALIBUR Iron Removal

EXCALIBUR Metals Removal Technology can

also remove iron from certain crudes
Iron naphthenates
Inorganic iron oxides, sulfides

Sample Iron, ppm

Heavy Canadian Crude Oil 19.9
+ 30 ppm Additive in Crude Oil 2.2

(5% wash water rate, with 6 ppm emulsion breaking chemical)

Copyright 2005 Baker Petrolite Corporation. All rights reserved

EXCALIBUR Metals Removal Technology

Conclusions
A laboratory-tested, field proven process to remove calcium
from high Ca crude oils
Industry-leading EXCALIBUR Metals Removal Technology has
been used to remove up to 85% of crude oil calcium present as
calcium naphthenates
Significant economic benefits to the refiner
Good desalter performance is maintained
Desalter water injection and removal system corrosion and
scaling can be controlled
Minimal impact on waste water treatment plant
Laboratory screening tests can be used to predict EXCALIBUR
performance on specific crude oil blends

Copyright 2005 Baker Petrolite Corporation. All rights reserved